A novel method is developed for grafting carbon nanotubes (CNTs) onto the carbon fiber (CF) surface by use of dendrimers. CF surface is functionalized by an adsorbed dendrimers layer. After an oxidation treatment, CNTs with carboxyl, carbonyl or hydroxyl groups are grafted onto the amino-functionalized CFs via chemical interactions. Homogeneous multi-scale structures with different CNT densities and lengths are gained successfully. Functional groups and morphology of the resulting materials are examined by X-ray photoelectronspectroscopy (XPS), Fourier transform-infrared spectrometer (FTIR), and scanning electron microscopy (SEM).